Interfacial Engineering of Polymer Membranes with Intrinsic Microporosity for Dendrite‐Free Zinc Metal Batteries

• Published in: Angewandte Chemie 2024-12, Vol.136 (49), p.n/a
• Main Authors: Tan, Rui, He, Hongzhen, Wang, Anqi, Wong, Toby, Yang, Yilin, Iguodala, Sunshine, Ye, Chunchun, Liu, Dezhi, Fan, Zhiyu, Furedi, Mate, He, Guanjie, Guldin, Stefan, Brett, Dan J. L., McKeown, Neil B., Song, Qilei
• Format: Article
• Language: English
• Subjects: Anodes; Cathodic protection; Coating; Decomposition reactions; Dendrites; Electrode materials; Electrolytic cells; Energy storage; Hydrogen evolution reactions; Ion-selective membranes; Membranes; Microporosity; Polymers; Polymers of intrinsic microporosity; Redox potential; Zinc; Zinc metal batteries; Zinc sulfate
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202409322

Metallic zinc has emerged as a promising anode material for high‐energy battery systems due to its high theoretical capacity (820 mAh g−1), low redox potential for two‐electron reactions, cost‐effectiveness and inherent safety. However, current zinc metal batteries face challenges in low coulombic efficiency and limited longevity due to uncontrollable dendrite growth, the corrosive hydrogen evolution reaction (HER) and decomposition of the aqueous ZnSO4 electrolyte. Here, we report an interfacial‐engineering approach to mitigate dendrite growth and reduce corrosive reactions through the design of ultrathin selective membranes coated on the zinc anodes. The submicron‐thick membranes derived from polymers of intrinsic microporosity (PIMs), featuring pores with tunable interconnectivity, facilitate regulated transport of Zn2+‐ions, thereby promoting a uniform plating/stripping process. Benefiting from the protection by PIM membranes, zinc symmetric cells deliver a stable cycling performance over 1500 h at 1 mA/cm2 with a capacity of 0.5 mAh while full cells with NaMnO2 cathode operate stably at 1 A g−1 over 300 cycles without capacity decay. Our work represents a new strategy of preparing multi‐functional membranes that can advance the development of safe and stable zinc metal batteries. Polymers of intrinsic microporosity (PIMs) containing hydrophilic Tröger's base groups were coated as ultrathin selective membranes on zinc metal anodes to regulate the ion transport and electrochemical reactions at interfaces. The PIM membranes regulate the zinc ion transport and effectively mitigate zinc dendrite growth, as well as reduce corrosive side reactions, leading to safe and stable zinc metal batteries.